Phenolate and phenoxyl radical complexes of Cu(ii) and Co(iii), bearing a new redox active N,O-phenol-pyrazole ligand

摘要

The synthesis and characterisation of the new N,O-phenol-pyrazole pro-ligand, pzLH, comprising a pyrazole covalently linked to an o,p-di-tert-butyl-substituted phenol, are herein reported. In CH _2Cl_2 at room temperature, the cyclic voltammogram (CV) of ~(pz)LH exhibits a quasi-reversible one-electron oxidation process (at E_(1/2) = 0.66 V vs. Fc~+/Fc) attributed to the formation of the phenoxyl radical cation [~(pz)LH]~+. ~(pz)LH reacts with M~(II)(BF_4)_2 (M = Cu, Co) in a 2:1 ratio to afford the bis-Cu~(pz)L_2 (1) and tris-Co ~(pz)L_3 (2) complexes respectively. The X-ray structure of 1 reveals a Cu(ii) ion in a square-planar trans-Cu~(II)-N _2O_2 coordination environment whereas that of 2 consists of a Co(iii) ion with an octahedral mer-N_3O_3 coordination sphere; formed by the chelation of two (in 1) or three (in 2) N,O-bidentate phenolate ligands respectively. Both structures are preserved in CH _2Cl_2 solution, as revealed by their NMR (for 2) and EPR (for 1) data. The CVs of 1 and 2 consist of two (at E_(1/2): 0.43 and 0.58 V vs. Fc+/Fc) and three (E_(1/2) = 0.12, 0.54 and 0.89 V vs. Fc+/Fc) reversible one-electron oxidation processes, respectively. The one-electron electrochemical oxidation of 1 and 2 produces the oxidised species, 1~+ and 2~+, which are stable for several hours at room temperature under inert atmosphere in CH_2Cl _2. The UV/vis and EPR data obtained for 1~+ and 2 ~+ are unambiguously consistent with the latter being formulated as Cu(ii)- and Co(iii)-phenoxyl radical complexes, as [Cu~(II)(~(pz)L)(~(pz)L)]~+ and [Co~(III)(~(pz)L)(~(pz)L)_2]~+ respectively.